CN117976887A - High specific capacity disulfide polymer positive electrode material, preparation method thereof and battery - Google Patents

High specific capacity disulfide polymer positive electrode material, preparation method thereof and battery Download PDF

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CN117976887A
CN117976887A CN202410362901.9A CN202410362901A CN117976887A CN 117976887 A CN117976887 A CN 117976887A CN 202410362901 A CN202410362901 A CN 202410362901A CN 117976887 A CN117976887 A CN 117976887A
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positive electrode
electrode material
disulfide polymer
specific capacity
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CN117976887B (en
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石伟
曾绍忠
田宇超
叶超
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Shenzhen Taike Power System Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to a high specific capacity disulfide polymer positive electrode material, a preparation method thereof and a battery, wherein the method comprises the following steps: dissolving an organic monomer in a solvent to prepare a solution, adding a conductive carbon matrix, and uniformly stirring to form a precursor, wherein the organic monomer is a multi-mercapto organic substance with a lithium-intercalation active functional group, and the lithium-intercalation active functional group is provided with an aromatic heterocycle or an aromatic heterocycle derivative, a thick aromatic ring or a thick aromatic ring derivative, or a thick heterocycle derivative and has conjugated delocalization large pi bonds; and adding an oxidant into the precursor for oxidation to obtain the composite material of the disulfide polymer and the conductive carbon matrix. The disulfide polymer has pores and a larger specific surface area, so that the rapid transmission of lithium ions is facilitated, and the composite conductive carbon matrix has the advantages of overlapping two effects, effectively improving the electronic conductivity of the composite material, and enabling the composite material to have the performances of high conductivity, rapid charge and discharge, excellent cycle stability and the like.

Description

High specific capacity disulfide polymer positive electrode material, preparation method thereof and battery
Technical Field
The invention relates to the technical field of battery anode materials, in particular to a high specific capacity disulfide polymer anode material, a preparation method thereof and a battery.
Background
Lithium ion batteries are widely used in smart phones, notebook computers and electric vehicles due to their excellent properties such as high energy density, long life, high voltage, etc. Along with the development of light and thin smart phones and notebook computers, multifunction, large screen and electric automobiles, the energy density requirements on batteries are higher and higher. However, conventional lithium ion batteries based on intercalation compounds have been developed for nearly thirty years, and their energy density has reached its limit and the rise space is very limited. Therefore, various novel battery systems with high energy density are applied and become research hotspots in various countries in the world, wherein organic electrode materials only contain light elements with rich resource reserves of carbon, hydrogen, nitrogen, sulfur, phosphorus and the like, the specific capacity of the organic electrode materials can reach 946mAh/g (cyclohexanedione), and the organic electrode materials have various structures and become one of the research hotspots.
The types of active functional groups in organic electronic materials that function as redox groups can be divided into four broad categories: 1. organic substances containing carbon-oxygen double bond or carbon-nitrogen double bond, such as p-benzoquinone, o-benzoquinone, polyhydroxy anthraquinone, calixarene oxide, polyimide, oxidized PHFR, conjugated lithium sulfonamide and the like; 2. polymers containing polysulfide linkages such as sulfurized polyacrylonitrile, sulfurized cyanuric acid, sulfurized polyaniline, sulfurized 1, 3-m-phenylenediyl, sulfurized fennel, dimercaptothiophene oxide, and phenylhexathiophenol oxide; 3. a free radical polymer. 4. Small organic molecules containing cyano groups and nitro groups, and the like. Although these organic electrode materials have a high theoretical specific capacity, they have the following problems: the conductivity is low, and a stable and ordered frame structure is not present like inorganic crystals in the charge and discharge process, so that the rate capability is low, and the cyclic stability is poor, the tap density is low, the voltage is low, the raw materials are expensive or the synthesis is difficult due to the fact that a small molecular organic material is easy to dissolve in electrolyte.
Disclosure of Invention
In view of the above, the high specific capacity disulfide polymer positive electrode material with high conductivity, fast charge and discharge and excellent cycle stability, the preparation method and the battery thereof are provided, multiple pores and larger specific surface area can be endowed by the disulfide polymer, the pores and the large specific surface area are favorable for fast transmission of lithium ions, and the conductive carbon matrix is compounded, so that the two effects are overlapped, and the electron conductivity of the composite material is effectively improved.
The preparation method of the high specific capacity disulfide polymer positive electrode material comprises the following steps:
dissolving an organic monomer in a solvent to prepare a solution, adding a conductive carbon matrix, and uniformly stirring to form a precursor, wherein the organic monomer is a multi-mercapto organic substance with a lithium-intercalation active functional group, and the lithium-intercalation active functional group is provided with an aromatic heterocycle or an aromatic heterocycle derivative, a thick aromatic ring or a thick aromatic ring derivative, or a thick heterocycle derivative and has conjugated delocalization large pi bonds;
and (3) adding an oxidant into the precursor for oxidation to obtain the composite material of the disulfide polymer and the conductive carbon matrix.
Preferably, the lithium intercalation active functional group is selected from at least one of benzoquinone group, cyano substituent-containing phenyl group, pyrazine group, anthraquinone group, naphthoquinone group and thiazole group, the organic monomer is dimercapto organic matter, trimercapto organic matter or organic matter with more than four mercapto groups, and the organic monomer is selected from at least one of tetramercapto pyrazine, tetramercapto benzoquinone, tetramercapto phthalonitrile, tetramercapto anthraquinone, dimercapto naphthoquinone, cyanuric acid and 2, 5-dimercaptothiadiazole.
Preferably, the conductive carbon matrix is at least one of acetylene black, ketjen black, carbon nanotubes, graphene and vapor grown carbon fibers, and the oxidant is at least one of air, sodium percarbonate, sodium peroxodisulfate, sodium perborate, hydrogen peroxide and iodine.
Preferably, the solvent is water, water is added for dissolution, then alkali metal hydroxide solid is added for stirring and dissolution, so that the multi-mercapto organic matter forms alkali metal salt corresponding to the multi-mercapto organic monomer in the solvent, the precursor is mixed liquid, the oxidant is dropwise added while stirring the mixed liquid, the composite particles are obtained after the oxidation reaction is completed, the filtering is carried out, and the alkali metal hydroxide solid is selected from NaOH or KOH.
Preferably, the solvent is an organic solvent, the organic solvent is used for dissolving an organic monomer to form a clear solution, then a conductive carbon matrix is added, stirring is carried out uniformly, spray drying is carried out, powder is obtained, the powder is transferred into a furnace, heating and heat preservation are carried out in air for a preset time, and the composite material is obtained, wherein the temperature is increased to 100-400 ℃.
Preferably, the solvent is an organic solvent, the organic solvent is used for dissolving an organic monomer to form a clear solution, then a conductive carbon matrix is added, stirring is carried out uniformly, spray drying is carried out, the obtained powder is transferred into a high-pressure reaction kettle, a solid oxidant or a gaseous oxidant is added, sealing is carried out, heating and heat preservation are carried out for a preset time, and the composite material is obtained, wherein the temperature is increased to 100-400 ℃.
Preferably, the mass ratio of the organic monomer to the conductive carbon matrix is 4:6-9:1, and the more preferred range is 5:5-8:2.
The invention also provides a battery, which comprises a positive electrode material, a binder and a conductive agent mixed and molded in a predetermined proportion, wherein the positive electrode material is prepared by the preparation method of the high specific capacity disulfide polymer positive electrode material.
Preferably, the mass ratio of the disulfide polymer to the conductive agent is 2:8-9:1, the conductive agent is acetylene black or graphene, and the preferable ratio range is 5:5-8:2.
The invention also provides a positive electrode material which is prepared by the preparation method of the high specific capacity disulfide polymer positive electrode material.
In the preparation method of the high-specific-capacity disulfide polymer positive electrode material and the battery, since the disulfide polymer has a certain pore and a large specific surface area, the pore and the large specific surface area are beneficial to the rapid transmission of lithium ions, and the conductive carbon matrix is compounded, the two effects are overlapped, and the electronic conductivity of the composite material is effectively improved. In addition, electrons and lithium ions can be rapidly transmitted in the composite material, so that the composite material has ultra-fast charge and discharge capacity of 50 ℃ at most, has excellent cycling stability, the specific capacity of 3000 times of cycling is still more than 100mAh/g, and the method is suitable for synthesizing the composite material of other organic sulfides and a conductive matrix, is a universal method and has wide application range.
Drawings
Fig. 1-5 show the chemical structure, lithium intercalation reactivity and corresponding theoretical lithium intercalation specific capacities of five representative disulfide polymers in the examples of the present invention.
The (a) in fig. 6-the (c) in fig. 6 are schematic diagrams of the composite structures of the disulfide polymer and the (a) hollow carbon spheres, (b) nanotubes, and (c) graphene sheets, respectively, wherein the bar in fig. 6, the (b) tube inner filler in fig. 6, and the (c) upper layer particles in fig. 6 represent the disulfide polymer, and the sphere shell in fig. 6, the (b) tube wall in fig. 6, and the (c) lower layer particles in fig. 6 are carbon materials.
FIG. 7 is an XRD pattern for OTTCA (oxidized cyanuric acid), OTTCA/G, and graphene.
FIG. 8 is a nitrogen adsorption curve for OTTCA, OTTCA/G and graphene.
Fig. 9 is the pore size distribution of OTTCA, OTTCA/G and graphene.
FIG. 10 is FT-IR spectra of TTCA (cyanuric acid), OTTCA/G and graphene.
FIG. 11 is a graph of the first charge and discharge performance of OTTCA/G in a 1M 1M LiPF 6 electrolyte.
FIG. 12 is a plot of specific capacity and coulombic efficiency for OTTCA/G at 1C cycles over different voltage ranges.
Fig. 13 is a first charge-discharge curve for pure OTTCA at 0.2 and 0.5C.
FIG. 14 is a representative SEM image of (a) - (c) OTTCA; (d) - (f) graphene; (G) - (i) OTTCA/G.
Detailed Description
The present invention will be described in detail with reference to specific embodiments and drawings.
The embodiment of the invention provides a preparation method of a high specific capacity disulfide polymer positive electrode material, which comprises the following steps:
S01, dissolving an organic monomer in a solvent to prepare a solution, adding a conductive carbon matrix, and uniformly stirring to form a precursor, wherein the organic monomer is a multi-mercapto organic matter with a lithium-intercalation active functional group, and the lithium-intercalation active functional group is provided with an aromatic heterocycle or an aromatic heterocycle derivative, a thick aromatic ring or a thick aromatic ring derivative, or a thick heterocycle derivative and has conjugated delocalization large pi bonds;
S02, adding an oxidant into the precursor for oxidation to obtain the composite material of the disulfide polymer and the conductive carbon matrix.
Preferably, the lithium intercalation active functional group is selected from at least one of benzoquinone group, cyano substituent-containing phenyl group, pyrazine group, anthraquinone group, naphthoquinone group and thiazole group, the organic monomer is dimercapto organic matter, trimercapto organic matter or organic matter with more than four mercapto groups, and the organic monomer is selected from at least one of tetramercapto pyrazine, tetramercapto benzoquinone, tetramercapto phthalonitrile, tetramercapto anthraquinone, dimercapto naphthoquinone, cyanuric acid and 2, 5-dimercaptothiadiazole. More preferably, the organic monomer is selected from the group consisting of tetramercaptopyrazine, tetramercaptobenzoquinone, tetramercaptophthalonitrile, tetramercaptoanthraquinone, dimercapto naphthoquinone, all of which have dicarbonyl groups, dicyano groups, and six-membered rings, exhibiting a stronger lithium intercalation activity.
The disulfide polymers are DSP for short, as shown in figures 1-5, and are the chemical structures, lithium intercalation reaction formulas and corresponding theoretical lithium intercalation specific capacities of five representative disulfide polymers DSP-1 to DSP-5 in the embodiment of the invention. The monomer of the DSP-1 is tetra-mercapto benzoquinone, each monomer has 4 mercapto groups, and six Li ions can be combined in the lithium intercalation reaction. The monomer of the DSP-2 is tetra-mercapto phthalonitrile quinone, each monomer has 4 mercapto groups, and six Li ions can be combined in the lithium intercalation reaction. The monomer of the DSP-3 is tetra-mercapto pyrazine, each monomer has 4 mercapto groups, and four Li ions can be combined in the lithium intercalation reaction. The monomer of DSP-4 is tetra-mercapto anthraquinone, each monomer has 4 mercapto groups, and six Li ions can be combined in the lithium intercalation reaction. The monomer of DSP-5 is dimercapto naphthoquinone, each monomer has 2 mercapto groups, and four Li ions can be combined in the lithium intercalation reaction. It is known that the composite material of the dithio polymer and the conductive carbon matrix has a plurality of mercapto groups, and can combine more Li ions in the lithium intercalation reaction, especially the composite material with dicarbonyl groups and dicyano groups can combine more Li ions.
Preferably, the conductive carbon matrix is at least one of acetylene black, ketjen black, carbon nanotubes, graphene, vapor grown carbon fibers. As shown in fig. 6, the disulfide polymer can be uniformly compounded with the conductive carbon matrix. For example, when (a) in fig. 6 is combined with the hollow carbon sphere, the particles can be uniformly distributed in the hollow carbon sphere shell, when carbon nanotubes are used, the particles can be filled in the carbon nanotubes (fig. 6 (b)), and when graphene is used, since graphene is a substantially planar layered body, the disulfide polymer has six-membered rings and the like, and can be combined and tiled as a planar layer of the carbon six-membered rings of graphene (fig. 6 (c)). The inventors found through experimental study that the effect of selecting highly conductive multi-layer graphene is rather better than that of single-layer graphene, for example, the effect of multi-layer graphene (about 10 layers) is compared with that of single-layer graphene, and found that the specific capacity and rate performance of the former are much higher than those of the latter. The ketjen black also has a good compounding effect, for example, the ketjen black product model is ECP-600JD, and can compound disulfide polymers with mass fraction as high as 90%. When nanoribbons or wires, such as carbon fibers, are employed, the dithio polymer also uniformly dispersedly mixes the linear carbon nanomaterial. Therefore, the disulfide polymer and the conductive carbon matrix are combined two by two, so that the disulfide polymer and the conductive carbon matrix have a strong composite nano-size effect. Because the disulfide polymer has a certain pore and a larger specific surface area, the conductive carbon matrix also has a larger specific surface area and a nano pore, and the pores and the large specific surface area are beneficial to the rapid transmission of lithium ions, and the conductive carbon matrix is compounded, the two effects are overlapped, and the electron conductivity of the composite material is effectively improved.
The oxidizing agent is preferably at least one of air, sodium percarbonate, sodium peroxodisulfate, sodium perborate, hydrogen peroxide, and iodine. The multi-mercapto polymerization of the organic monomer is linked by an oxidant to form a disulfide polymer, and the following oxidation reaction process is illustrated by using trisodium thiocyanate as an example, and the reaction equation is as follows:
In step S01, an organic monomer is dissolved in a solvent to prepare a solution, and a conductive carbon matrix is added and stirred uniformly to form a precursor. Preferably, the precursor is a mixed solution, and the oxidant is dropwise added while stirring the mixed solution for reaction for 1-24 hours. Preferably, the solvent comprises water, water is added for dissolution, then alkali metal hydroxide solid is added, stirring is carried out for dissolution, so that the multi-mercapto organic matter forms alkali metal salt corresponding to the multi-mercapto organic monomer in the solvent, filtering is carried out after the oxidation reaction is finished, the filter residue is washed with water and alcohol, and the composite particles are obtained after drying, wherein the alkali metal hydroxide solid is selected from NaOH or KOH, and can be other alkali metal hydroxides which are easy to participate in the reaction. The mass ratio of the organic monomer to the conductive carbon matrix is 4:6-9:1, and the preferable range is 5:5-8:2.
As shown in the above reaction formula, the organic monomer is sodium salt, and after oxidation by the oxidant, the polysulfide is formed by polymerization and linkage between the polysulfide groups. The structure of the disulfide polymer is in a net shape or a linear shape, for example, the number of mercapto groups in the organic monomer exceeds 3, so that a net-shaped disulfide polymer is formed, and the dimercapto monomers form linear polymers, for example, DSP-1 to DSP-4 in fig. 1-4, respectively, with four mercapto groups, can form a net structure, and are more beneficial to electron transmission. Whereas the two thiols form a line like DSP-5 in fig. 5.
In step S02, there are at least three embodiments of the oxidation method.
The first method is a liquid method, and the specific process is as follows: dissolving an organic monomer in a solvent to prepare a solution, specifically dissolving in water, adding an alkali metal hydroxide solid, dissolving for a preset time, adding a conductive carbon matrix, uniformly stirring, dropwise adding an oxidant solution under stirring, reacting for a certain time after the addition, filtering after the reaction is finished, washing with water, washing with ethanol, and drying to obtain the composite material. And then mixing the polysulfide polymer and the conductive agent, wherein the mass ratio of the polysulfide polymer to the conductive agent is 2:8-9:1, and the preferable ratio range is 5:5-8:2, and then manufacturing the button cell.
The second method is a high-temperature air oxidation gas phase method, and the specific process is as follows: dissolving an organic monomer in a solvent to prepare a solution, dissolving the solution in the specific solvent, reacting the solution in the same way as the first step, adding the conductive carbon matrix, uniformly stirring, and spray-drying to obtain the composite particles of the monomer and the conductive carbon matrix. And (3) placing the composite particles into a muffle furnace, heating to a certain temperature, and oxidizing the monomers into a disulfide bond by using air, wherein the common oxidation temperature is 100-400 ℃. The subsequent steps for manufacturing the battery are the same as those described above.
The third is an autoclave oxidation gas phase method, which comprises the following specific processes: dissolving an organic monomer in a solvent to prepare a solution, dissolving the solution in the specific solvent, reacting the solution in the same way as the first step, adding the conductive carbon matrix, uniformly stirring, and spray-drying to obtain the composite particles of the monomer and the conductive carbon matrix. And (3) placing the composite particles into an autoclave, and oxidizing the organic monomer at a certain temperature, preferably 100-400 ℃, by using sublimed sulfur or iodine. The subsequent steps for manufacturing the battery are the same as those described above.
The embodiment of the invention also provides a battery, which comprises a positive electrode material, a binder and a conductive agent mixed and molded in a predetermined proportion, wherein the positive electrode material is prepared by the preparation method of the high-specific-capacity disulfide polymer positive electrode material, and the battery is prepared by the same steps.
In yet another aspect, the embodiment of the invention provides a positive electrode material, which is prepared by the preparation method of the high specific capacity disulfide polymer positive electrode material.
FIG. 7 is an XRD pattern for OTTCA (oxidized cyanuric acid), OTTCA/G, and graphene. The graph shows that the compounded disulfide polymer positive electrode material has stronger absorption peak and more obvious crystal phase.
FIG. 8 is a nitrogen adsorption curve for OTTCA, OTTCA/G and graphene. As can be seen from the figure, the compounded disulfide polymer positive electrode material has a higher nitrogen adsorption capacity than the single polymer OTTCA.
Fig. 9 is the pore size distribution of OTTCA, OTTCA/G and graphene. As can be seen from the graph, the average particle size of the compounded disulfide polymer positive electrode material is lower than that of the single polymer OTTCA, the pore size distribution is more in the range of 1-3nm, and the pore size number below 10nm is obviously more than that of the single polymer OTTCA. Thus, better nano-size effect can be shown, and the nano performance of the compounded disulfide polymer positive electrode material is better, so that the beneficial effects described above are demonstrated.
Fig. 10 is FT-IR spectra of TTCA (cyanuric acid), OTTCA (cyanuric acid after sulfur oxidation, employed), OTTCA/G (cyanuric acid/graphene after oxidation), and graphene. Compared with a single polymer OTTCA, the disulfide polymer after compounding shows that after compounding graphene, the conjugated effect still exists, so that the vibration frequency moves to a low wave number, the positions of 2900-3300cm - are absent or weaker, the positions of 1530cm -, 1120cm - and the like are weaker, N-H is proved to be substituted, no N-H stretching vibration absorption peak exists, disulfide (ether group) exists in the disulfide polymer after compounding, a small amount of C=S bonds are proved, and certain compounding of graphite and the disulfide polymer exists, and chemical action exists.
FIG. 11 is a graph showing the first charge and discharge performance of OTTCA/G in a 1M 1M LiPF6 electrolyte. The figure shows that the disulfide polymer phase OTTCA/G after compounding has better first charge and discharge performance, and can also keep better specific capacity at higher voltage of 1.8-3.5V after secondary or tertiary charge and discharge.
FIG. 12 is a plot of specific capacity and coulombic efficiency for OTTCA/G at 1C cycles over different voltage ranges. As can be seen, the compounded dithio polymer phase OTTCA/G exhibits good specific capacity and coulombic efficiency over all three voltage ranges when cycled at 1C.
Fig. 13 is a first charge-discharge curve for pure OTTCA at 0.2 and 0.5C. As is clear from the graph, the compounded disulfide polymer phase OTTCA/G was excellent in both charge and discharge properties at 0.2 and 0.5C, and did not change much differently.
FIG. 14 is a representative SEM image of (a) - (c) OTTCA; (d) - (f) graphene; (G) - (i) OTTCA/G. From the electron microscope image, the compounded disulfide polymer phase OTTCA/G is closer to the microstructure of the pure graphene, which shows that the disulfide polymer phase OTTCA/G and the microstructure of the pure graphene are mutually dispersed after being compounded, can be well fused, and has better nano-size performance.
The following examples illustrate the preparation of high specific capacity disulfide polymer positive electrode materials, and various aspects of the positive electrode materials and battery performance.
Example 1
1. Preparing a composite material: adding 2.08 g of tetramercapto pyrazine into 100 g of water, adding 1.60 g of NaOH, stirring and dissolving to obtain a clear solution, adding 0.5g of acetylene black into the solution, stirring uniformly, continuously stirring and adding an ethanol solution of iodine (5.08 g of iodine is dissolved in 50 g of ethanol), stirring and reacting for 10 hours, filtering, washing with water, washing with ethanol, and drying at 80 ℃ to obtain 2.51 g of product for later use.
2. Electrochemical performance test: mixing the obtained positive electrode material, a binder (polyvinylidene fluoride) and a conductive agent (acetylene black) uniformly according to a mass ratio of 80:10:10, adding a solvent, grinding into uniform slurry, scraping and coating the slurry on an aluminum foil, drying, punching into a wafer with a diameter of 12mm, tabletting, drying, and assembling into a button cell, wherein a counter electrode is a metal lithium sheet, an electrolyte is a general lithium-sulfur cell electrolyte, a current for charge and discharge test is 400 mA/g, a first lithium intercalation capacity is 498: 498 mAh/g, a first efficiency is 91%, and a specific capacity after 100 times of circulation is 357 mAh/g.
Example two
1. Preparing a composite material: adding 2.36 g of tetra-mercapto benzoquinone into 100 g of water, adding 1.60 g of NaOH, stirring and dissolving to obtain a clear solution, adding 4.0 g of carbon nano tubes into the solution, stirring uniformly, adding 2.27 g of 30% hydrogen peroxide solution under continuous stirring, stirring and reacting for 2 hours, filtering, washing with water, washing with ethanol, and drying at 80 ℃ to obtain 6.23 g of product for later use.
2. Electrochemical performance test: mixing the obtained positive electrode material, a binder (polyvinylidene fluoride) and a conductive agent (acetylene black) uniformly according to a mass ratio of 80:10:10, adding a solvent, grinding into uniform slurry, scraping and coating the slurry on an aluminum foil, drying, punching into a wafer with the diameter of 12mm, tabletting, drying, and assembling into a button cell, wherein a counter electrode is a metal lithium sheet, an electrolyte is a general lithium-sulfur cell electrolyte, a current for charge-discharge test is 400 mA/g, a first lithium intercalation capacity is 659mAh/g, a first efficiency is 87%, and a specific capacity after 100 times of circulation is mAh/g.
Example III
1. Preparing a composite material: 2.56 g of tetra-mercapto terephthalonitrile is taken and added into 100 g of water, 2.51 g of graphene is added into the solution, the solution is stirred uniformly, sodium percarbonate solution (2.07 g of sodium percarbonate is dissolved in 50g of water) is added under continuous stirring, the reaction is stirred for 24 hours, and the 5.07 g of product is obtained after filtering, water washing, ethanol washing and 80 ℃ drying for standby.
2. Electrochemical performance test: mixing the obtained positive electrode material, a binder (polyvinylidene fluoride) and a conductive agent (acetylene black) uniformly according to a mass ratio of 80:10:10, adding a solvent, grinding into uniform slurry, scraping and coating the slurry on an aluminum foil, drying, punching into a wafer with a diameter of 12mm, tabletting, drying, and assembling into a button cell, wherein a counter electrode is a metal lithium sheet, an electrolyte is a general lithium-sulfur cell electrolyte, a current for charge-discharge test is 400 mA/g, a first lithium intercalation capacity is 418 mAh/g, a first efficiency is 85%, and a specific capacity after 100 times of circulation is 372 mAh/g.
Example IV
1. Preparing a composite material: adding 1.50 g of 2, 5-dimercaptothiadiazole into 100 g of water, adding 0.80 g of NaOH, stirring and dissolving to obtain a clear solution, adding 13.5 g of ketjen black into the solution, stirring uniformly, adding a sodium peroxodisulfate solution (4.76 g of sodium peroxodisulfate is dissolved in 50 g of water) under continuous stirring, stirring and reacting for 2 hours, filtering, washing with water, washing with ethanol, drying at 80 ℃ to obtain 14.73 g of product for later use.
2. Electrochemical performance test: mixing the obtained positive electrode material, a binder (polyvinylidene fluoride) and a conductive agent (acetylene black) uniformly according to a mass ratio of 80:10:10, adding a solvent, grinding into uniform slurry, scraping and coating the slurry on an aluminum foil, drying, punching into a wafer with a diameter of 12mm, tabletting, drying, and assembling into a button cell, wherein a counter electrode is a metal lithium sheet, an electrolyte is a general lithium-sulfur cell electrolyte, a current for charge-discharge test is 400 mA/g, a first lithium intercalation capacity is 356 mAh/g, a first efficiency is 86%, and a specific capacity after 100 times of circulation is 290 mAh/g. The material has excellent multiplying power performance, the specific capacity is still more than 82 mAh/g after 10C cycles for 5000 times (see figure 7 for details), and even the specific capacity is still more than 40mAh/g under 50C multiplying power.
Example five
1. Preparing a composite material: adding 1.77 g of cyanuric acid into 100 g of water, adding 1.20 g of NaOH, stirring and dissolving to obtain a clear solution, adding 3.0 g of vapor grown carbon fiber into the solution, stirring uniformly, adding 1.70 g of 30% hydrogen peroxide under continuous stirring, stirring and reacting for 4 hours, filtering, washing with water, washing with ethanol, drying at 80 ℃ to obtain 4.65 g of product for later use.
2. Electrochemical performance test: mixing the obtained positive electrode material, a binder (polyvinylidene fluoride) and a conductive agent (acetylene black) uniformly according to a mass ratio of 80:10:10, adding a solvent, grinding into uniform slurry, scraping and coating the slurry on an aluminum foil, drying, punching into a wafer with the diameter of 12mm, tabletting, drying, and assembling into a button cell, wherein a counter electrode is a metal lithium sheet, an electrolyte is a general lithium-sulfur cell electrolyte, a current for charge-discharge test is 400 mA/g, a first lithium intercalation capacity is 478 mAh/g, a first efficiency is 83%, and a specific capacity after 100 times of circulation is 249 mAh/g.
Example six
1. Preparing a composite material: adding 2.08 g of tetramercapto pyrazine into 100 g of water, adding 1.60 g of NaOH, stirring and dissolving to obtain a clear solution, adding 0.5g of acetylene black into the solution, stirring uniformly, continuously stirring and adding an ethanol solution of iodine (5.08 g of iodine is dissolved in 50 g of ethanol), stirring and reacting for 10 hours, filtering, washing with water, washing with ethanol, and drying at 80 ℃ to obtain 2.51 g of product for later use.
2. Electrochemical performance test: mixing the obtained positive electrode material, a binder (polyvinylidene fluoride) and a conductive agent (acetylene black) uniformly according to a mass ratio of 80:10:10, adding a solvent, grinding into uniform slurry, scraping and coating the slurry on an aluminum foil, drying, punching into a wafer with a diameter of 12mm, tabletting, drying, and assembling into a button cell, wherein a counter electrode is a metal lithium sheet, an electrolyte is a general lithium-sulfur cell electrolyte, a current for charge and discharge test is 400 mA/g, a first lithium intercalation capacity is 498: 498 mAh/g, a first efficiency is 91%, and a specific capacity after 100 times of circulation is 357 mAh/g.
Example seven
1. Preparing a composite material: adding 1.77 g of cyanuric acid into 100 g of tetrahydrofuran, stirring and dissolving to obtain a clear solution, adding 2.0 g of ketjen black into the solution, stirring uniformly, spray-drying to obtain black powder, transferring the black powder into a muffle furnace, heating to 250 ℃ in air, preserving heat for 6 hours, and weighing 3.0 g of the powder product for later use.
2. Electrochemical performance test: mixing the obtained positive electrode material, a binder (polyvinylidene fluoride) and a conductive agent (acetylene black) uniformly according to a mass ratio of 80:10:10, adding a solvent, grinding into uniform slurry, scraping and coating the slurry on an aluminum foil, drying, punching into a wafer with a diameter of 12mm, tabletting, drying, and assembling into a button cell, wherein a counter electrode is a metal lithium sheet, an electrolyte is a general lithium-sulfur cell electrolyte, a current for charge-discharge test is 400 mA/g, a first lithium intercalation capacity is 443 mAh/g, a first efficiency is 81%, and a specific capacity after 100 times of circulation is 226 mAh/g.
Example eight
1. Preparing a composite material: adding 1.77 g of cyanuric acid into 100g of tetrahydrofuran, stirring and dissolving to obtain a clear solution, adding 2.0 g of ketjen black into the solution, stirring uniformly, spray-drying to obtain black powder, weighing 3.0g of the powder, uniformly mixing with 3.81 g of iodine, transferring into a 100mL reaction kettle, sealing, transferring into an oven, heating to 100 ℃, preserving heat for 6 hours, and weighing 6.0 g of the powder for later use.
2. Electrochemical performance test: mixing the obtained positive electrode material, a binder (polyvinylidene fluoride) and a conductive agent (acetylene black) uniformly according to a mass ratio of 80:10:10, adding a solvent, grinding into uniform slurry, scraping and coating the slurry on an aluminum foil, drying, punching into a wafer with a diameter of 12mm, tabletting, drying, and assembling into a button cell, wherein a counter electrode is a metal lithium sheet, an electrolyte is a general lithium-sulfur cell electrolyte, a current for charge-discharge test is 400 mA/g, a first lithium intercalation capacity is measured to be 425 mAh/g, a first efficiency is 85%, and a specific capacity after 100 times of circulation is 191 mAh/g.
Example nine
1. Preparing a composite material: adding 2.56 g of tetra-mercapto terephthalonitrile into 100g of N-methylpyrrolidone, stirring and dissolving to obtain a clear solution, adding 3.0 g of ketjen black into the solution, stirring uniformly, spray-drying to obtain black powder, uniformly mixing with 1.0 g of sublimed sulfur powder, transferring into a10 mL all-stainless steel high-temperature reaction kettle, sealing, transferring into a muffle furnace, heating to 400 ℃, preserving heat for 6 hours to obtain a bright black caking product, taking out and grinding, and weighing 5.0 g of the product for later use.
2. Electrochemical performance test: mixing the obtained positive electrode material, a binder (polyvinylidene fluoride) and a conductive agent (acetylene black) uniformly according to a mass ratio of 80:10:10, adding a solvent, grinding into uniform slurry, scraping and coating the slurry on an aluminum foil, drying, punching into a wafer with a diameter of 12mm, tabletting, drying, and assembling into a button cell, wherein a counter electrode is a metal lithium sheet, an electrolyte is a general lithium-sulfur cell electrolyte, a current for charge-discharge test is 400 mA/g, a first lithium intercalation capacity is 587 mAh/g, a first efficiency is 76%, and a specific capacity after 100 times of circulation is 373 mAh/g.
The test properties after the positive electrode materials obtained according to examples 1 to 9 described above were fabricated into electrodes are shown in table 1 below.
TABLE 1 composition ratios of examples 1-9 and performance data tested after electrode formation
Organic monomers Solvent(s) Conductive carbon matrix Oxidizing agent Reaction time Product(s) And (3) a positive electrode: bonding: conductive agent Electric current Lithium intercalation capacity First time efficiency Specific capacity after 100 cycles
Example 1 2.08G of tetramercaptopyrazine Water + NaOH 0.5G acetylene black Ethanol solution of iodine 10h 2.51g 80:10:10 400 mA/g 498 mAh/g 91% 357 mAh/g
Example 2 2.36 G of tetramercaptobenzoquinone Water + NaOH 4.0 G carbon nanotubes Hydrogen peroxide solution 2h 6.23 G 80:10:10 400 mA/g 659 mAh/g 87% 491mAh/g
Example 3 2.56 G of tetra-mercapto terephthalonitrile Water + NaOH 2.51 G graphene Sodium percarbonate solutions 24h 5.07 G 80:10:10 400 mA/g 418 mAh/g 85% 372 mAh/g
Example 4 1.50 G of 2, 5-dimercaptothiadiazole Water + NaOH 13.5 G Keqin black Sodium peroxodisulfate solution 2h 14.73 G 80:10:10 400 mA/g 356mAh/g 86% 290 mAh/g
Example 5 1.77 G of cyanuric acid Water + NaOH 3.0 G of vapor grown carbon fiber Hydrogen peroxide 1.70 g 4h 4.65 G 80:10:10 400 mA/g 478 mAh/g 83% 249mAh/g
Example 6 2.08G of tetramercaptopyrazine Water + NaOH 0.5G acetylene black Ethanol solution of iodine 10h 2.51g 80:10:10 400 mA/g 498 mAh/g 91% 357 mAh/g
Example 7 1.77 G of cyanuric acid Tetrahydrofuran (THF) 2.0 G Keqin black Spray drying, muffle furnace+air 6H+250 degree 3.0g 80:10:10 400 mA/g 443 mAh/g 81% 226mAh/g
Example 8 1.77 G of cyanuric acid Tetrahydrofuran (THF) 2.0 G Keqin black Powder + iodine, reaction kettle + oven 6H+100 degree 6.0g 80:10:10 400 mA/g 425 mAh/g 85% 191mAh/g
Example 9 2.56 G of tetra-mercapto terephthalonitrile N-methylpyrrolidone 3.0 G Keqin black Spray drying, muffle furnace+air 6H+400 degree 5.0g 80:10:10 400 mA/g 587mAh/g 76% 373mAh/g
It should be noted that the present invention is not limited to the above embodiments, and those skilled in the art can make other changes according to the inventive spirit of the present invention, and these changes according to the inventive spirit of the present invention should be included in the scope of the present invention as claimed.

Claims (10)

1. The preparation method of the high specific capacity disulfide polymer positive electrode material is characterized by comprising the following steps of:
dissolving an organic monomer in a solvent to prepare a solution, adding a conductive carbon matrix, and uniformly stirring to form a precursor, wherein the organic monomer is a multi-mercapto organic substance with a lithium-intercalation active functional group, and the lithium-intercalation active functional group is provided with an aromatic heterocycle or an aromatic heterocycle derivative, a thick aromatic ring or a thick aromatic ring derivative, or a thick heterocycle derivative and has conjugated delocalization large pi bonds;
and (3) adding an oxidant into the precursor for oxidation to obtain the composite material of the disulfide polymer and the conductive carbon matrix.
2. The method for preparing the high specific capacity disulfide polymer positive electrode material according to claim 1, wherein the lithium intercalation active functional group is at least one selected from benzoquinone group, cyano substituent-containing phenyl group, pyrazine group, anthraquinone group, naphthoquinone group and thiazole group, the organic monomer is dimercapto organic matter, trimercapto organic matter or more than tetramercapto organic matter, and the organic monomer is at least one selected from tetramercapto pyrazine, tetramercapto benzoquinone, tetramercapto phthalonitrile, tetramercapto anthraquinone, dimercapto naphthoquinone, cyanuric acid and 2, 5-dimercaptothiadiazole.
3. The method for preparing a high specific capacity disulfide polymer positive electrode material according to claim 2, wherein the conductive carbon matrix is at least one of acetylene black, ketjen black, carbon nanotubes, graphene and vapor phase grown carbon fibers, and the oxidant is at least one of air, sodium percarbonate, sodium peroxodisulfate, sodium perborate, hydrogen peroxide and iodine.
4. The method for preparing a high specific capacity disulfide polymer positive electrode material according to claim 1, wherein the solvent is water, water is added for dissolution, then alkali metal hydroxide solid is added, stirring and dissolution are carried out, so that the multi-mercapto organic matter forms alkali metal salt corresponding to the multi-mercapto organic monomer in the solvent, the precursor is mixed solution, the oxidant is dropwise added while stirring the mixed solution, filtering is carried out after the oxidation reaction is finished, and the alkali metal hydroxide solid is selected from NaOH or KOH after washing and drying.
5. The method for preparing a high specific capacity disulfide polymer positive electrode material according to claim 1, wherein the solvent is an organic solvent, the organic solvent dissolves an organic monomer to form a clear solution, then a conductive carbon matrix is added, the mixture is stirred uniformly, spray-dried to obtain powder, the powder is transferred into a furnace, and the temperature is raised to 100-400 ℃ in the air for a preset time to obtain the composite material.
6. The method for preparing the high specific capacity disulfide polymer positive electrode material according to claim 1, wherein the solvent is an organic solvent, the organic solvent is used for dissolving an organic monomer to form a clear solution, then a conductive carbon matrix is added, stirring is uniform, spray drying is carried out, the obtained powder is transferred into a high-pressure reaction kettle, a solid oxidant or a gaseous oxidant is added, sealing is carried out, and heating and heat preservation are carried out for a preset time, so that the composite material is obtained, wherein the temperature is increased to 100-400 ℃.
7. The method for preparing the high specific capacity disulfide polymer positive electrode material according to claim 1, wherein the mass ratio of the organic monomer to the conductive carbon matrix is 4:6-9:1.
8. A battery comprising a positive electrode material, a binder, and a conductive agent mixed and molded in a predetermined ratio, wherein the positive electrode material is prepared by the method for preparing a high specific capacity disulfide polymer positive electrode material according to any one of claims 1 to 7.
9. The battery of claim 8, wherein the mass ratio of the disulfide polymer to the conductive agent is between 2:8 and 9:1, and the conductive agent is acetylene black or graphene.
10. A positive electrode material, characterized in that the positive electrode material is produced by the method for producing a high specific capacity disulfide polymer positive electrode material according to any one of claims 1 to 7.
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